Ampholytic ter-polymers for use in personal care compositions

ABSTRACT

Novel ampholytic ter-polymers comprising at least an ethylenically unsaturated cationic monomer, a monomer containing a carboxylic acid or sulfonic acid group and diallyamine or derivative are claimed. Further, the ter-polymers may be used in personal care or personal washing compositions optionally in the presence of conditioning agents such as silicone, fatty amines, fatty amine oxides and fatty quaternaries and/or various benefit agents. The ter-polymer compositions are especially useful in the treatment of keratin-containing substrates. Keratin substrates include, but are not limited to, animal and human hair, skin and nails.

This application is a continuation of U.S. Ser. No. 12/711,589, filedFeb. 24, 2010 now granted, which claims the benefit of ProvisionalApplication Nos. 61/209,293, filed Mar. 5, 2009 and 61/300,658, filedFeb. 2, 2010 herein all incorporated entirely by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel ampholytic ter-polymers, personalcare compositions containing said ter-polymers and methods for usingsuch ter-polymers. The herein described ampholytic ter-polymers compriseat least an ethylenically unsaturated cationic monomer, a monomercontaining a carboxylic acid or sulfonic acid group and a diallyamine ordiallyamine derivative. The ter-polymers and ter-polymer compositions ofthe present invention are useful in the treatment of keratin-containingsubstrates. Keratin substrates include, but are not limited to, animaland human hair, skin and nails.

Hair is composed of keratin, a sulfur-containing fibrous protein. Theisoelectric point of keratin, and more specifically of hair, isgenerally in the pH range of 3.2-4.0. Therefore, at the pH of a typicalshampoo, hair carries a net negative charge. Consequently, cationicpolymers have long been used as conditioners in shampoo formulations, oras a separate conditioning treatment to improve the wet and drycombability of the hair. The substantivity of the cationic polymers fornegatively charged hair along with film formation facilitates detanglingduring wet hair combing and a reduction in static flyaway during dryhair combing. Cationic polymers generally also impart softness andsuppleness to hair.

Although cationic polymers and amphoteric polymers have long been usedas conditioners in personal care compositions such as shampoos andbodywashes, the commercially available polymers are deficient inproviding a certain combination of effects on keratinic substrates. Forinstance, a certain number of claims related to cationic and amphotericpolymers described in the literature focus, either on a limited numberof attributes for the conditioning process such as friction reductionand softness, or on the ability of the polymers to act as depositionaids for silicone only. These type of polymers are disclosed in U.S.Pat. Nos. 5,573,709, 5,977,038, 6,200,554, 6,451,298, 5,302,322,6,348,188 B1, EP 0 529 883 B1, and U.S. Application Publication Nos.2006/0123564 and 2005/0002871 herein incorporated entirely by reference.

The shortcomings in the performance of current commercial conditioningpolymers have prompted the search for new polymeric materials that willmake possible the achievement of a true “2 in 1” conditioning shampoo.Thus, in the area of hair and skin care in particular, there is a needfor cationic polymers that will display simultaneously the followingcharacteristics: 1) They should be able to act as deposition aids notonly for silicone but also for a wide range of other conditioningactives on keratinic substrates, 2) The polymers should be able toprovide by themselves basic conditioning effects to keratinic substrateswithout the need of any additional conditioning ingredient, and 3) Theyshould be capable of interacting with other conditioning actives toprovide conditioning synergies leading to additional and novelconditioning functionalities, i.e. refatting of hair/skin, eliminationof hair “squeakiness” after washing, reduced irritation, improvedemolliency, softness, wet and dry friction reduction and shine.

The achievement of these three effects with one single cationic polymerposes, however, major technical challenges. This is especially true in“2 in 1” washing or cleansing compositions where the processes ofcleansing and deposition are antagonistic in nature; i.e. the cleansingprocess not only will tend to remove the polymer from the keratinicsubstrate but also any other conditioner material that deposits on itssurface.

The present inventors have successfully designed amphoteric ter-polymersthat are able to perform the three tasks described above withoutaffecting the washing process. While not wishing to be bound by theory,it is believed each monomer unit in the ter-polymer backbone has aspecific functionality. For instance, the cationic moieties in theter-polymer are substantive to negative keratinic substrates from thewashing compositions, and in addition allow complexation with anionicsurfactants. Furthermore, complexation of the ter-polymer with otherconditioning materials such as fatty amines and cationic surfactants isachieved by the presence of an anionic monomer unit. Finally, a certaindegree of hydrophobicity and polarity for conditioning andmoisturization is attained with a third monomer unit formed fromdiallyamine or derivatives of diallyamine.

With the above described monomer composition the ter-polymer can alsoform in situ coacervate complexes with the washing composition. Thesecomplexes have the appropriate rheology to deposit lubricious layers ofter-polymer/surfactant that aid in the deposition of conditioningactives by flocculation. With these characteristics, when the ampholyticter-polymers are formulated into washing and rinse-off compositions theyhave the following properties: 1) The amphoteric ter-polymers of theinvention have a strong affinity for keratin substrates even in thepresence of anionic surfactants, 2) By being slightly hydrophobic andpolar they can provide conditioning on their own, 3) Because of theirability to form simultaneously complexes with anionic, fatty amines, andcationic surfactants they can provide enhanced and addedfunctionalities. For instance, as the ter-polymers are able to depositlayers of polymer/fatty moieties on the keratinic substrates they canalso act as refatting agents reducing the effect of “hair squeakiness”characteristic of shampooed hair. This later feature is mostly absent inall polymers used in personal care described so far in the literature.

The use of the ter-polymer in cleansing or washing compositions solves,the precipitation difficulties often encountered when cationicsurfactants are added to formulations containing anionic surfactants. 4)Finally, because of their ability to form complex coacervates, theter-polymers can also act as deposition aids for silicone and other oilswhen combined with them. Thus, not only do the polymers work effectivelyas conditioners by themselves on keratinic substrates but also theyfunction as deposition agents for fatty amines, fatty quaternaries,silicone, and other conditioning oils from cleansing and rinse-offcompositions providing lubricity, softness, styling manageability, andan overall conditioning synergy to keratinic substrates.

2. Brief Description of the Background Art

Cationic and ampholytic conditioning polymers are known for use inpersonal care compositions.

Cationic homopolymers are specifically known to have thickening effectson formulations and also to be good as conditioning agents for hair andskin. For example, SALCARE SC 96 is a homopolymer of methacryloylethyltrimethylammonium chloride available from Ciba Corporation, Tarrytown,N.Y. It is a well known as a thickener in personal care compositions.

U.S. Publication Application Nos. 2008/0057016, 2008/0206355,2005/202984 and U.S. Pat. No. 7,303,744 teach homopolymers ofacrylamidopropyltrimethyl ammonium chloride (APTAC) andmethacrylamidopropyltrimethyl ammonium chloride (MAPTAC) for use inshampoo formulations.

Cationic copolymers such as SALCARE SC60 (APTAC/acrylamide copolymer)available from Ciba Corporation, Tarrytown, N.Y., are taught for use onhair. For example, U.S. Pat. Nos. 5,543,074, 6,908,889, 6,858,202,6,696,053 and European Application No. 1 911 778 teach copolymers ofcationic monomers and acrylamide in hair formulations.

Amphoteric copolymers are also well known for use on hair. For example,U.S. Pat. Nos. 6,555,101, 6,82,776, 6,511,671, 4,814,101, 6,066,315,6,110,451, and 5,879,670 teach APTAC-acrylic acid copolymers for use inhair. Several U.S. Published application Nos. teaching similarcopolymers are 2005/0276778, 2003/0086894, 2003/0131424 and 2008/0033129and Canadian Application No. 2139495. Also cationic celluloses suchquaternized hydroxethyl cellulose and cationic guar gum are well knownfor use in hair.

Further, U.S. Pat. No. 6,348,188 B1, U.S. Pat. No. 6,706,258 B1, andEuropean Application Nos. EP 0 529 883 B1, EP 1 137 397 B1 and EP 0 158531 B1 teach various cationic polymers capable of depositing silicone onhair.

However, none of these patents or publications teach the inventiveamphoteric ter-polymer described herein nor do the above describedcationics or amphoterics show the multiple advantages of the presentamphoteric ter-polymer. The inventive ter-polymers offer a wider rangeof conditioning benefits to hair and skin than those previouslydescribed in the known art. The ter-polymers are especially useful in2-in-1 shampoos.

SUMMARY OF THE INVENTION

The present invention embodies novel conditioning polymers.

A conditioning polymer formed from

i.) a cationic monomer defined by formula (I)

in which:R₁ and R₂ are independently hydrogen or methyl,R₃, R₄ and R₅ are independently linear or branched C₁-C₃₀ alkylradicals,X is NH, NR₆ or oxygen,R₆ is C₁-C₆ alkyl,L is C_(n)H_(2n),n is an integer from 1 to 5,and A− is an anion derived from an organic or inorganic acid, such as amethosulphate anion or halide, such as chloride or bromide;ii.) at least one anionic monomer selected from the group consisting ofethylenically unsaturated carboxylic acid and sulfonic acid containingmonomers;andiii.) a diallyl amine monomer defined by formulae (II) or (III)

in which,R₇ and R₈ are independently hydrogen or C₁-C₄ alkyl,R₉ is hydrogen, branched or linear C₁-C₃₀ alkyl, C₁-C₃₀alkoxy,

hydroxy substituted C₁-C₁₀ alkyl, C₇-C₉alkylphenyl, carboxyalkyl,alkoxyalkyl and carboxyamidalkyl,R₁₀ is hydrogen, C₁-C₂₀ alkyl, C₅-C₁₀ cycloalkyl or an unsubstituted orsubstituted benzyl radical,with the proviso that if R₁₀ is other than hydrogen, then R₉ is

AO is a C₁-C₁₂ alkylene oxide or mixtures of two or more types of C₁-C₁₂alkylene oxides, it being possible for the two or more types to beattached to one another in block form or in random form,m is an integer from 2 to 200,R₁₁ is hydrogen or methyl;and(iv) optionally, a crosslinking monomer;wherein the formed ter-polymer is optionally at least partiallyneutralized with a fatty amine, fatty amine oxide or fatty quaternary.

What is meant by the proviso that if R₁₀ is other than hydrogen meansthat Formula (III) is not for example, diallydimethyammonium chloride(DADMAC).

The invention also encompasses personal cleansing or personal carecompositions comprising the conditioning polymer described above.

The personal care compositions of particular interest are those personalcare compositions which are applied to the body, including the skin andhair.

These personal care or personal cleansing compositions comprising theconditioning polymer described above may be dispersed or soluble in acosmetically acceptable medium which medium optionally further comprisesa detersive anionic surfactant and/or a silicone.

Personal cleansing or personal care compositions comprising theconditioning polymer described above may further comprise at least onesurfactant chosen from anionic, amphoteric, nonionic and zwitterionicsurfactants. Preferably, the surfactant is an anionic detersivesurfactant.

The personal cleansing or personal care compositions of particularinterest are personal cleansing compositions which are shampoos orbodywashes.

Of special interest are “2 in 1” shampoos containing the inventiveter-polymer.

Thus a shampoo or bodywash, preferably a 2 in 1 shampoo comprising theconditioning ter-polymer described above which shampoo or bodywashoptionally further contains a detersive anionic surfactant and/or asilicone are claimed.

Several method embodiments are envisioned.

A process for washing and/or conditioning a keratinous substratecomprising treating the keratinous substrate with an effective amount ofa composition comprising the polymer described above, optionally furthercomprising an anionic surfactant and/or a silicone.

A method for enhancing the deposition of silicone, fatty quaternaries,fatty amines, fatty amine oxides and other conditioning actives ontoskin, hair or nails which comprises topically applying to said skin,hair or nails a composition comprising

i.) the polymer described above;

ii) at least one silicone compound

and

optionally,

an effective amount of a benefit agent to a desired location on theskin, hair, and/or nails.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients or reaction conditions usedherein are to be understood as modified in all instances by the term“about”.

“Molecular weight” means average molecular weight (Mw) expressed asg/mole.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified.

Monomers are ethylenically unsaturated compounds capable of beingpolymerized.

A monomer unit is the unit that is formed from the ethylenicallyunsaturated compound after polymerization.

Amphoteric or ampholytic may be used interchangeably, and describe apolymer that comprises anionic monomeric units and cationic monomericunits. An ampholytic polymer may be: anionic at a pH that is higher thanits isoelectric point; and cationic at a pH that is lower than itsisoelectric point: wherein the isoelectric point is the pH at which thenet charge on a polymer is zero.

(Meth)acryl refers to both the acrylic and methacrylic derivatives.

The term “polymer” as used herein shall include materials whether madeby polymerization of one type of monomer or made by two (i.e.,copolymers) or more types of monomers.

The term “ter-polymer” for purposes of the invention means a polymerformed from at least three different monomers.

The term “water soluble” as used herein, means that the polymer issoluble in water in the present composition. In general, the polymershould be soluble at 25° C. at a concentration of 0.1% by weight of thewater solvent, preferably at 1%, more preferably at 5% and mostpreferably at 15%.

Keratinous substrates are human or animal skin, hair or nails.

The term “skin” as used herein includes the skin on the face, neck,chest, back, arms, hands, legs and scalp.

As used herein, the term “effective amount” refers to that amount of acomposition necessary to bring about a desired result, such as, forexample, the amount needed to condition a keratin-containing substrate.

The compositions of the present invention preferably comprise acosmetically acceptable vehicle or carrier. This phrase “cosmeticallyacceptable vehicle or carrier”, as used herein, means one or morecompatible solid or liquid fillers, diluents, extenders and the like,which are cosmetically acceptable. As used herein “cosmeticallyacceptable” means a material (e.g., compound or composition) which issuitable for use in contact with human skin, hair or nails. The type ofcarrier or vehicle utilized in the present invention depends on the typeof product desired. The compositions useful in the present invention maybe a wide variety of product types. These include, but are not limitedto, shampoos, rinse-off conditioners, lotions, creams, gels, sprays,pastes, mousses, and suspensions.

The Conditioning Ter-Polymer

The novel conditioning polymer of the invention is formed from at leastthree monomers,

i.) a cationic monomers encompassed by formula (1),

in which:R₁ and R₂ are independently hydrogen or methyl,R₃, R₄ and R₅ are independently linear or branched C₁-C₃₀ alkylradicals,X is NH, NR₆ or oxygen, preferably X is NH or NR₆ and most preferably Xis NH,R₆ is C₁-C₆ alkyl,L is C_(n)H_(2n),n is an integer from 1 to 5,and A− is an anion derived from an organic or inorganic acid, such as amethosulphate anion or halide, such as chloride or bromide,ii.) at least one anionic monomer selected from the group consisting ofethylenically unsaturated carboxylic acid and sulfonic acid containingmonomers;andiii.) a diallyl amine defined by formulae (II) or (III)

in which,R₇ and R₈ are independently hydrogen or C₁-C₄ alkyl,andR₉ is hydrogen, branched or linear C₁-C₃₀ alkyl,

C₁-C₃₀alkoxy, hydroxy substituted C₁-C₁₀ alkyl, C₇-C₉alkylphenyl,carboxyalkyl, alkoxyalkyl and carboxyamidalkyl,R₁₀ is hydrogen, C₁-C₂₀ alkyl, C₅-C₁₀ cycloalkyl or an unsubstituted orsubstituted benzyl radical, preferably R₁₀ is hydrogen, C₁-C₄ alkyl orbenzyl, most preferably R₁₀ is hydrogen;with the proviso that if R₁₀ is other than hydrogen, then R₉ is

AO is a C₁-C₁₂ alkylene oxide or mixtures of two or more types thereof,it being possible for the two or more types to be attached to oneanother in block form or in random form,n is an integer from 2 to 200,R₁₁ is hydrogen or methyl;andiv.) optionally a crosslinking monomer,wherein the formed ter-polymer is optionally at least partiallyneutralized or complexed with a fatty amine, fatty amine oxide or fattyquaternary.

In regard to formula (I), R₃, R₄ and R₅ are for example C₁-C₁₄, C₁-C₈,C₁-C₆ or C₁-C₄. Most typically R₃, R₄ and R₅ are C₁-C₄ such as methyl,ethyl, propyl, butyl or a mixture thereof.

The cationic monomer of formula (I) used in the inventive conditioningter-polymer is for example selected from the group consisting of(meth)acryloyloxyethyl-N,N,N-trimethylammonium chloride,(meth)acryloyloxyethyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate,(meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate,(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride,(meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium monoethylsulfate, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniumchloride, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniummonomethyl sulfate and mixtures thereof,

preferably (meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride,(meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium monoethylsulfate, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniumchloride, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniummonomethyl sulfate and mixtures thereof andespecially acryloylaminopropyl-N,N,N-trimethylammonium chloride.X is preferably NH.

The cationic monomer of formula (I) or component i.) will for examplemake up at least about 10 to about 98 weight percent of the formedconditioning ter-polymer.

Alternatively, for example the cationic monomer of formula (I) makes upabout 40 to about 96 or about 40 to about 94 weight percent of the totalweight of the formed ter-polymer. A minimum of about 40 or 50 weight %component i.) is most typical.

The anionic monomers of component ii.) will typically contain carboxylicacids or sulfonic acid groups. For example, acrylic acid (AA),methacrylic acid (MAA), 2-acrylamido-2-methylpropane sulfonic acid(AMPSA), 2-methacrylamido-2-methylpropane sulfonic acid (MAMPSA),crotonic acid, 2-methyl crotonic acid, maleic acid, maleic anhydride,itaconic acid, itaconic anhydride and mixtures thereof are considered.

For example, the conditioning ter-polymer is formed from anionicmonomers of component ii.) which are monoethylenically unsaturated C₃-C₆monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonicacid, isocrotonic acid, 2-ethylpropenoic acid or ethylenicallyunsaturated C₄-C₆ dicarboxylic acids, such as maleic acid, fumaric acid,itaconic acid or the anhydrides thereof, for example maleic anhydride,or the sodium, potassium or ammonium salts thereof.

The anionic monomer of component ii.) are especially compounds offormula (VI) or the anhydrides thereof:

whereR₁₂ and R₁₃ are independently hydrogen or C₁-C₆alkyl,R₁₄ is hydrogen, C₁-C₆alkyl or a COOM group andM is hydrogen, a monovalent or divalent metal ion, ammonium or anorganic ammonium ion.

A particularly preferred embodiment is the conditioning polymer, whereinthe anionic monomer of component ii.) is a compound of formula (VI) orthe anhydrides thereof:

R₁₂ and R₁₃ are independently hydrogen or C₁-C₆alkyl,R₁₄ is hydrogen, C₁-C₆alkyl or a COOM group,M is hydrogen, a monovalent or divalent metal ion, ammonium or anorganic ammonium ion,R₉ and R₁₀ of the diallyl component iii.) are hydrogenandthe formed ter-polymer is at least partially neutralized with a fattyamine or a fatty amine oxide.

The anionic monomer or component ii.) will preferably make up at least 2to about 25, about 4 to about 20, about 5 to about 15 weight percent ofthe total weight of the formed conditioning polymer.

Most often component ii.) will more preferably not exceed 20 or 30 wt.%. For example, the component ii) will most often be a minimum of about3 or 4 wt. % and a maximum of about 20 wt. %.

The molar ratio of component i.) and ii.) may vary from 12:1 to 3:1,preferably for example 10:1 to 4:1. Thus the ter-polymer will alwayscarry a cationic charge regardless of the pH of the medium in which theter-polymer is dispersed or dissolved.

Component iii.) monomer is for example diallyamine.

The amine of the diallyamine may be substituted by R₉ and/or R₁₀.

R₉ is defined as hydrogen, branched or linear C₁-C₃₀ alkyl,

C₁-C₃₀alkoxy, hydroxy substituted C₁-C₁₀ alkyl, C₇-C₉-phenylalkyl,carboxyalkyl, alkoxyalkyl and carboxyamidalkyl.

* represents the connection to the nitrogen of the diallyamine.

Linear or branched C₁-C₃₀ alkyl is for example alkyl having C₁-C₄,C₁-C₆, C₁-C₈, C₁-C₁₀, C₁-C₁₂, C₁-C₁₄, C₁-C₁₆, C₁-C₁₈, C₁-C₂₀, C₁-C₂₂,C₁-C₂₄, C₁-C₂₆ or C₁-C₂₈. Specific examples include methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, lauryl, cetyl,octadecyl, icosyl or docosyl.

C1-C₁₂ alkylene oxide is for example CH₃—O—CH₂—, CH₃—(O—CH₂CH₂—)₂O—CH₂—,CH₃—(O—CH₂CH₂—)₃O—CH₂— or CH₃—(O—CH₂CH₂—)₄O—CH₂—.

For example R₉ may be substituted by polyethyleneoxide orpolypropyleneoxide or a mixture thereof.

Such substituted alkyoxylated diallyamines are disclosed in U.S. Pat.Nos. 7,579,421 and 5,478,883 herein incorporated entirely by reference.

For example, formulae (II) or (III) may be a monomer, wherein R₉ is

AO is C₁-C₁₂ alkylene oxide or a mixture of two or more types thereof,it being possible for the two or more types to be attached to oneanother in block or in random form,m is an integer from 1 to 200,and R₁₁ is hydrogen or methyl.

The diallyamine may be compounds of formula (II) or (III):

A particularly preferred monomer of (II) or (III) is

wherein AO is C₂-C₄ alkylene oxide such as ethylene oxide, propyleneoxide, 1-butylene oxide, isomers of butylene oxide and mixtures thereofit being possible for the two or more types of alkylene oxides to beattached to one another in block or in random form,R₈ and R₇ are as defined above,and R₁₁ is hydrogen or methyl.

A preferred monomer formula of (IIa) or (IIIa) is formed by the reactionof diallyamine with about 10 to 30 wt. percent propylene oxide and about90 to 70 wt. percent ethylene oxide and the average molecular weight ofthe diallyamine of formula (IIa) and (IIIa) is about 500 to about 3500.

Another especially preferred compound of formula (II) is diallyamine,wherein R₉ is hydrogen

and formula (III) is the protonated salt (R₉ and R₁₀ are hydrogen).

C₇-C₉-phenylalkyl is for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl.

Carboxyalkyl is for example —COCH₂CH₃, —CO(CH₂)_(n)CH₃, wherein n is1-4, 1-6, 1-8, 1-10, 1-12 or 1-16, or —COCH₂CH(CH₃)₂. Thus the alkyl ofcarboxyalkyl may be branched or linear and will vary in carbon numberfrom C₂-C₂₄, C₂-C₂₀, C₂-C₁₈, C₂-C₁₂, C₂-C₈ or C₂-C₆.

Carboxyamidalkyl is analogous to carboxyalkyl above. Carboxylamidalkylis for example, —CONCH₂CH₃, —CON(CH₂)_(n)CH₃, wherein n is 1-4, 1-6,1-8, 1-10, 1-12 or 1-16, or —COCH₂CH(CH₃)₂. Thus the alkyl ofcarboxyalkyl may be branched or linear and will vary in carbon numberfrom C₂-C₂₄, C₂-C₂₀, C₂-C₁₈, C₂-C₁₂, C₂-C₈ or C₂-C₆.

carbons.

Alkoxyalkyl is for example, ethoxyethyl, propoxymethyl, methoxymethyl,methoxyethyl, ethoxybutyl, ethoxyoctyl etc. The carbon number of thealkoxy will for examples vary from C₁-C₆. The alkyl of the alkoxyalkylwill for example vary from C₁-C₁₈, C₁-C₁₂, C₁-C₈ or C₁-C₆.

Hydroxy substituted C₁-C₁₀ alkyl is for example —CH2CH2-OH,—CH2CH2CH2OH, —CH2CH(OH)CH2CH2OH. The alkyl of the C₁-C₁₀ alkyl may forexample range from C₁-C₈, C₁-C₆, C₁-C₄. or C₁-C₂. The alkyl forinstance, may be mono, di or tri hydroxyl substituted.

Suitable diallyamines of formula (II) are for example diallyamine,diallymethylamine, diallyethylamine, diallypropylamine,diallybutylamine, diallyhydroxymethylamine, diallyhydroxyethylamine,diallyhydroxypropylamine, diallylethoxyethylamine anddiallyhydroxylbutylamine.

Diallyamines do not function as crosslinking agents although themonomers are diolefinic. Instead the monomer polymerizes to form apyrrolidine ring as part of the polymer backbone as below.

Component iii.) may make up about 2.0 to about 40 weight percent ormakes up for example about 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 18, 20,30 or 35 weight percent of total weight of the formed polymer.

The component iii.) may make up from about 2 to about 40, about 3 toabout 35, or about 3 to about 30 weight percent of the total weight offormed polymer.

The weight percent of component iii.) in the formed terpolymer willdepend very much on the molecular weight of the component iii). Forexample when R₉ of component iii) is

the average molecular weight of the monomer may vary from 500 to 3500.

When the conditioning ter-polymer is formed from monomers such as (IIa)and (IIIa)

the polymerized monomer units of IIa and/or IIIa make up from about 6 or7 to about 35, 8 to about 30 wt. percent of the formed conditioningter-polymer.

Further (IIa) and (IIIa) monomers have surfactant properties. Thealkylene oxide substituted monomers show a hydrophilic-lipophilicbalance which is determined by the particular C₁-C₁₂ alkylene oxide andthe number of repeating units. The preferred monomers of (IIa) and(IIIa) used to form the conditioning ter-polymer are characterized by anHLB from 5 to about 18.

The diallyamine monomer component iii.) of formula (IIa) and (IIIa)above is characterized by an average molecular weight (via GPC) of about500 to about 3500, preferably from about 800 to about 3000 and mostpreferably from about 1000 to about 3000.

A particularly preferred conditioning polymer comprises a monomer offormula (IIa) or (IIIa) formed by the reaction of diallyamine with about10 to 30 wt. percent propylene oxide and about 90 to 70 wt. percentethylene oxide.

Further the conditioning ter-polymer formed using the diallyaminemonomer component iii.) of formula (IIa) and (IIIa) above ischaracterized by a hydrophilic-lipophilic balance of between 5 and 18,preferably 6 to 17.

HLB values are calculated using Davis equation that uses the groupcontributions:HLB=7+ΣH(hydrophilic group numbers)−ΣL(lipophilic group numbers)where ΣH is the sum of contributions of hydrophilic groups, and ΣL isthe sum of contributions of hydrophobic groups.

The calculation methods are further described within Davis, J. T.,Rideal, E. K. Interfacial Phenomena 1963, 2^(nd) Ed., Academ. Press,London and Davis, J. T. Proc. Int. Congr. Surf. Act. 2^(nd), 1957, 1,426-438.

The formed ter-polymer will for example carry a net positive charge.This net positive charge is primarily due to the monomer unit of formula(I) and is independent of the ter-polymer matrix or formulationenvironment. However, the diallyamine monomer unit may also contributeto the total cationic charge of the formed ter-polymer when in an acidicenvironment. As shampoo formulations are typically slightly acidic ie. 5to about 6.5, the diallyamine monomer unit of formula (III) will likelybe protonated giving additional cationic charge to the formedter-polymer (R₁₀ will be hydrogen).

The total charge density of the formed ter-polymer will to some extentbe dependent on the pH of the medium. However, the charge density willvary from about 0.2 to about 6 or 7 mequiv./gram. For instance, thecharge density will vary from about 0.5 to about 6 or about 1 to about 5mequiv/gram. Typically the charge density of the ter-polymer in aslightly acidic environment will vary from about 1.0 to about 4.5 orabout 2 to about 3.8.

The negative charge (from the anionic monomer or component ii)) in theformed polymer may optionally be neutralized or form a complex orcoacervate with a fatty amine, a fatty amine oxide, or a fattyquaternary either by adding the fatty amines, oxides or fatty quaternaryduring the polymerization process or after the polymerization process.For example, the negative charge produced by the acidic monomer may beneutralized prior to polymerization then polymerized. Alternatively, thefatty amine, or fatty amine oxide, or fatty quaternary may simply beadded after formation of the amphoteric polymer. Preferably, the fattyamine, or fatty amine oxide, or fatty quaternary is added after theamphoteric polymer is formed if added at all.

Personal cleansing or personal care composition comprising theconditioning ter-polymer along with a conditioning agent in oneembodiment of the invention may exist in a complex coacervate form upondilution of water or upon addition of the inventive ter-polymer to theformulation. The coacervate may include complexation with theconditioning agents such as a fatty amine, fatty amine oxide, fattyquaternary defined below, silicone, oil, or emollient also definedbelow.

Fatty Amines, and Fatty Amine Oxides, and Fatty Quaternaries

These fatty amines are essentially cationic surfactants.

Fatty Amines

Fatty amines useful to compositions of the present invention includeprimary, secondary and tertiary amines.

Fatty amines or salts thereof having the formula

wherein R₁ is a C₈-C₃₀ straight or branched chain aliphatic,R₂ and R₃ are independently hydrogen, C₁-C₃₀ straight or branched chainaliphatic, hydroxyalkyl, amidoalkyl, carboxyalkyl, cyclic, alkoxy,polyalkoxy, or hydroxypolyalkoxy group function as useful fatty amines.For example, R₂ and R₃ are independently C₁-C₈ alkyl or C₁-C₆ alkyl.

Nonlimiting examples of the primary, secondary and tertiary fatty aminesthereof are octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, octadecylamine, laurylamine, myristylamine,stearylamine, eicosylamine, docosylamine, coco amine, oleylamine, tallowamine, hydrogenated-tallow amine, soya amine, dioctylamine,didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine,dicocoamine, dehydrogenated-tallow amine, dioctadecylamine,N-methyldioctadecylamine, N,N-dimethyldodecylamine,N,N-dimethylmyristylamine, N,N-dimethylstearylamine andN,N-dimethyloctadecylamine.

Myristylamine although defined as tetradecamine is more likely a blendof C₁₂, C₁₄ and C₁₆ homologues.

Stearylamine is analogous in that stearyl is octadecamine but is morelikely a blend of C₁₆, C₁₈ and C₂₀.

Laurylamine is defined as dodecylamine however is more likely a blend ofC₁₀, C₁₂ and C₁₄ homologues.

Mixtures of the above fatty amines may also be used.

Fatty Amine Oxides

Long chain tertiary amine oxides corresponding to the following generalformula:

wherein R₁ contains an alkyl, alkenyl or monohydroxy alkyl radical offrom about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties, and from 0 to about 1 glyceryl moiety, and R₂ and R₃ containfrom about 1 to about 3 carbon atoms and from 0 to about 1 hydroxygroup, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropylradicals. The arrow in the formula is a conventional representation of asemipolar bond.

Non-limiting examples of amine oxides suitable for use in this inventioninclude dimethyl-dodecylamine oxide, oleyidi(2-hydroxyethyl)amine oxide,dimethyloctylamine oxide, dimethyl-decylamine oxide,dimethyl-tetradecylamine oxide, 3,6,9-tri-oxaheptadecyldiethylamineoxide, di(2-hydroxyethyl)-tetradecylamine oxide,2-dodecoxyethyldimethylamine oxide,3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide,dimethylhexadecylamine oxide, myristyldimethyl amine oxide andstearyldimethyl amine oxide.

Fatty Quaternaries

Suitable cationic surfactants for charge neutralization of theter-polymer are mono- and dialkyl quats corresponding to the followingformula.

Mono long chain alkyl quats suitable for use herein include Formula (VI)conditioning surfactants wherein R₁, R₂, and R₃, which may be the sameor different, are C₁-C₄ alkyl groups (ie. ethyl or methyl) and R₄ is aC₈ or greater aliphatic hydrocarbyl group (preferably C₁₄ to C₂₂ alkyl).Other alkyl quats suitable for use herein are Formula (VI) conditioningsurfactants wherein R₁ and R₂, which may be the same or different, areC₁-C₄ alkyl groups (ie. ethyl or methyl), R₃ is an aryl group, forexample benzyl, and R₄ is a C₈ or greater aliphatic hydrocarbyl group(for example C₁₄ to C₂₂ alkyl). [A] can be chloride, bromide, ormethosulfate. The monoalkyl quats may, but need not, be in the form ofmixtures. Non-limiting examples of mono alkyl quats are:

cetyltrimethylammonium chloride (C16);

stearyltrimethylammonium chloride (C18);

behenyltrimethylammonium chloride (C22);

cetyltrimethylammonium bromide (C16);

tallowtrimonium chloride (C16/C18);

behenyltrimethylammonium methosulfate (C22);

palmityltrimethylammonium chloride (C16);

hydrogenated tallowtrimethylammonium chloride (C16/C18);

hydrogenated tallowtrimethylammonium bromide (C16/C18);

hydrogenated tallowtrimethylammonium methosulfate (C16/C18);

cetrimonium tosylate (C16): and

eicosyltrimethylammonium chloride (C20).

Also included in Formula (VI) are dialkyl quats in which R₁ and R₂,which may be the same or different, are C₁-C₄ alkyl groups and R₃ andR₄, which may be the same or different, are C₈ or greater aliphatichydrocarbyl groups (for example C₁₄ to C₂₂ alkyl). If desired, thedialkyl quats may be in the form of mixtures. Non-limiting examples ofdialkyl quats are:

dimethyldicetylammonium chloride (C16);

dimethyldistearylammonium chloride (C18);

dimethyldipalmitylammonium chloride (C16);

dimethyl(dihydrogenatedtallow)ammonium chloride (C16/C18);

dimethyl(ditallow)ammonium chloride (C16/C18)

dimethyl(dihydrogenatedtallow)ammonium bromide (C16/C18)

dimethyl(dihydrogenatedtallow)ammonium methosulfate (C16/C18)

Desirably, the level of cationic surfactant to neutralize theter-polymer varies from about 0.1 to about 5 percent by weight, based onthe total weight of the ter-polymer. In the practice of this invention,the cationic surfactants can also be mixtures of monoalkyl quats anddialkyl quats wherein the ratio of the monoalkyl quat to dialkyl quat isfrom 15:1 to 1:0.5, more particularly from 0:1 to 1:1 are of particularinterest.

The weight ratio of fatty quaternary, fatty amine or fatty amine oxideto ter-polymer may vary for example, from about 1:5 to about 5:1,alternatively about 1:3 to about 3:1 or more typically about 1:2 toabout 1:2.

The novel amphoteric ter-polymer may comprise additional monomers otherthan those defined by the monomer groups i.), ii.) and iii.).

For example the amphoteric polymer may optionally also containadditional nonionic monomers, For example the amphoteric polymer mayoptionally also contain at least one monomer selected from the groupconsisting of C₁-C₂₂ straight or branched chain alkyl acrylates ormethacrylates, a C₁-C₂₂ straight or branched chain n-alkyl acrylamide ormethacrylamide, C₁-C₆ hydroxy substituted alkyl acrylates ormethacrylates, n-vinylpyrrolidone, vinyl acetate, ethoxylated andpropoxylated acrylate or methacrylate and unsubstituted acrylamide.

Suitable nonionic monomers which may optionally be polymerized with themonomers of components i.), ii.) and iii.) are for example acrylamide,hydroxyethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide,N,N-diethyl(meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl(meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate and octyl (meth)acrylate.

The amphoteric polymer may also optionally contain amine containingmonomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, dimethylaminopropyl (meth)acrylamide, diethylaminoethyl(meth)acrylamide, 2-tert.-butylaminoethyl (meth)acrylate ordimethylaminoneopentyl (meth)acrylate.

Preferably, the amphoteric ter-polymer is formed substantially frommonomer units i.), ii.) and ii.) above and optionally crosslinkingagents and/or neutralized with fatty amine, fatty amine oxide or fattyquaternaries.

The weight ratio of the conditioning polymer and fatty amine, fattyamine oxide or fatty quaternary ranges from 1:5 to 5:1, preferably 1:3to 3:1 and most preferably 1:2 to 1:5. Substantially formed from monomerunits i.), ii.) and ii.) above and optionally crosslink agents and/orneutralized with fatty amine, fatty amine oxide or fatty quaternariesmeans that additional monomers other than those defined in i.), ii.) andiii.) and optional agents may be used to form the ter-polymer but willtypically be no more than about 2, 3, 4 or 5 weight percent of theformed ter-polymer.

The amphoteric ter-polymer may consist of monomer components i.), ii.)and iii.), wherein the formed ter-polymer is optionally at leastpartially neutralized or complexed with a fatty amine, fatty amine oxideor fatty quaternaries and further optionally contains a crosslinkingagent.

The average molecular weight (Mw) of the ampholytic conditioningter-polymer or mixtures thereof ranges for example from about 10,000 toabout 18,000,000, about 25,000 to about 5,000,000, typically about35,000 to about 1,800,000. Alternatively, the Mw may vary from about15,000 to about 1,000,000 or about 10,000 or about 20,000 to about800,000. For example, more preferably about 100,000 to about 1,000,000are envisioned.

The amphoteric polymer may be either water soluble, water-swellable orwater dispersible.

The conditioning amphoteric polymer may optionally be cross-linked.

“Cross-linked” as used herein refers to at least two chains of theamphoteric polymer attached by bridges, referred to herein as“cross-linking agents” comprising an element, a group, or a compoundwhich joins certain carbon atoms of the chains by primary chemicalbonds. Alternatively, the amine of the pyrrolidine (formed from thediallyl amine) incorporated into the chain of the formed conditioningpolymer may also be the site where the chains are joined. For example,U.S. Pat. No. 6,323,306, herein incorporated entirely by reference,teaches the cross-linking of cationic co-polymers with diallyl amineusing polyfunctional cross-linking agents.

“Polyfunctional” cross-linking agents may comprise monomers having: atleast two double bonds; at least a double bond and a reactive group; orat least two reactive groups.

Suitable cross-linking agents include, but are not limited to,polyfunctional epoxy compounds, dihaloalkyl compounds, diisocyanatecompounds and compounds containing at least two activated olefinicdouble bonds.

Exemplary cross-linking agents of the at least diolefinic variety aremethylenebisacrylamide; methylenebismethacrylamide; 1,3-diallylurea,triallylurea, tetraallylurea, N,N-diallylacrylamide, tetraallylammoniumchloride, tetraallylammonium sulfate, tetraallylammonium methylsulfate,esters of unsaturated monocarboxylic and polycarboxylic acids withpolyols, diacrylates and triacrylates, dimethacrylates andtrimethacrylates, butanediol and ethylene glycol diacrylate andmethacrylate, diethylene glycol diacrylate, poly(ethylene glycol)diacrylate, poly(propylene glycol) diacrylate and the like,trimethylolpropane triacrylate (TMPTA) and trimethylolpropanetrimethacrylate (TMPTMA). Allyl compounds may also be considered such asallyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polyallylesters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine;allyl esters of phosphoric acid; and/or vinylphosphonic acidderivatives. MBA is the most typical cross-linking agent.

Examples of polyfunctional epoxy compounds include epihalohydrins suchas epichlorohydrin, ethylene glycol diglycidyl either (EGDE); diglycidylether; 1,2,3,4-diepoxybutane; 1,2,5,6-diepoxyhexane; poly(propyleneglycol) diglycidyl ether (PPGDE); 1,4-butanediol diglycidyl ether,3-bis(glycidyloxy)methyl-1,2-propanediol, bisphenol A diglycidyl ether(BADGE), poly(phenylglycidyl ether-co-formaldehyde), glycerolpropoxylate triglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline,triglycidyl isocyanurate and the like.

Examples of dihaloalkyl compounds include 1,2-dichloroethane,1,2-dibromoethane, 1,3-dichloropropane, 1,4-dichlobutane,1,6-dichlorohexane, 1,10-dichlorodecane and the like. Preferreddihaloalkyl cross-linkers are 1,2-dibromoethane and 1,2-dichloroethane.

Diisocyanate compounds can be used as the cross-linking agent for basepolymers containing primary or secondary amino groups. Examples ofdiisocyanate compounds are isophorone diisocyanate (IPDI),1,4-diisocyanobutane, hexamethylene diisocyanate (HDI), toluenediisocyanate (TDI) and the like.

The polyfunctional cross-linking units may be added during the formationof the amphoteric polymer at amounts that range from 20 to 10,000 ppm ofthe total monomer content. For example, 20 to 1000 ppm, 50 to 800 ppm or75 to 600 ppm are envisioned.

Typical crosslinkers are methylenebisacrylamide (MBA);methylenebismethacrylamide.

The weight fraction of crosslinking comonomers, based on the total massof the copolymers, is not more than 5%, 3% or 2% by weight, moretypically from 0.00002 to 2% by weight, and most preferably from 0.00002to 1% by weight

Use of the Conditioning Ter-Polymer

The novel amphoteric ter-polymer may be used in virtually any personalcare composition. The amphoteric polymer has been found to be especiallyuseful in personal care compositions which are used on keratinoussubstrates such as hair, skin or nails. Such products as shampoos,conditioners, rinses, coloring products, bleaching products, settinglotions, blow-drying lotions, restructuring lotions, perms andstraightening products may incorporate the inventive amphoteric polymer.

These personal care compositions comprising the amphoteric polymer maybe personal cleansing compositions such as shampoos and bodywashes.

For example the cleansing composition comprising the conditioningter-polymer is a 2-in-1 shampoo, a bodywash, a facial wash, a bubblebath, soapless cleansers, liquid and bar soap; a shower gel, exfoliatingshower gel; a milk bath; moist towelletes; bath effervescent tablets(e.g., bubble bath); a bath/shower gel or a shower cream and may furthercomprises a detersive anionic surfactant from about 5% to about 50%,preferably from about 8% to about 30%, most preferably from about 10% toabout 25% and especially about 12% to about 18%, by weight of thecomposition.

Of particular interest are conditioning shampoos or 2-in-1 shampoos.These shampoos not only wash but also condition hair. Thus 2-in-1shampoos are advantageous in that they do not require a secondconditioning step after washing the hair.

Thus a preferred embodiment is a personal cleansing compositioncomprising the conditioning ter-polymer, wherein the cleansingcomposition is a 2-in-1 shampoo and further comprises a detersiveanionic surfactant from about 5% to about 50%.

“Bodywash” encompasses all cleansing vehicles applied to the body.Exemplary forms of cleansing vehicles include, but are not limited to,liquid, bar, gel, foam, aerosol or pump spray, cream, lotion, stick,powder, or incorporated into a patch or a towelette. In addition,soapless cleansers may be used as well. The bodywash can be made intoany suitable product form. Thus, as used herein, “bodywash” includes,but is not limited to, a soap including liquid and bar soap; a showergel; including an exfoliating shower gel; a foaming bath product (e.g.gel, soap or lotion); a milk bath; including a gel cleanser, a liquidcleanser and a cleansing bar; moist towelletes; bath effervescenttablets (e.g., bubble bath); a bath/shower gel; a shower cream.

These personal care compositions incorporating the amphoteric polymermay also be keratinous conditioning compositions such as hand lotions,body lotion, a body spray, mist or gel, hair conditions rinses, shavingcream, an after-shave, after-shave moisturizer, a depilatory cream; ashaving product e.g. a shaving cream, gel, foam or soap, an after-shave,after-shave moisturizer; a hand and nail cream and combinations thereof,and any other composition used for post-cleansing application to thebody, including the skin and hair.

Thus the personal care composition is a hand lotion, body lotion, a bodyspray, mist or gel, hair conditioning rinse, shaving cream, gel, foam orsoap, an after-shave, after-shave moisturizer, a hand and nail cream ora depilatory cream.

As implied above the personal care products can be in any form such ascreams, ointments, pastes, foams, gels, lotions, powders, make-ups,sprays, sticks or aerosols.

Creams are oil-in-water emulsions containing more than 50% of water. Theoil-containing base used therein is usually mainly fatty alcohols, forexample lauryl, cetyl or stearyl alcohol, fatty acids, for examplepalmitic or stearic acid, liquid to solid waxes, for exampleisopropyl-myristate or beeswax and/or hydrocarbon compounds, such asparaffin oil. Suitable emulsifiers are surfactants having primarilyhydrophilic properties, such as the corresponding non-ionic emulsifiers,for example fatty acid esters of polyalcohols of ethylene oxide adducts,such as polyglycerol fatty acid ester or polyoxyethylenesorbitan fattyacid ether (Tween trademarks); polyoxyethylene fatty alcohol ether ortheir esters or the corresponding ionic emulsifiers, such as the alkalimetal salts of fatty alcohol sulfonates, sodium cetyl sulfate or sodiumstearyl sulfate, which are usually used together with fatty alcohols,such as cetyl alcohol or stearyl alcohol. In addition, creams containagents which reduce water loss during evaporation, for examplepolyalcohols, such as glycerol, sorbitol, propylene glycol, and/orpolyethylene glycols.

Ointments are water-in-oil emulsions which contain up to 70%, preferablynot more than 20 to 50%, of water or of an aqueous phase. Theoil-containing phase contains predominantly hydrocarbons, such asparaffin oil and/or solid paraffin which preferably contains hydroxycompounds, for example fatty alcohol or their esters, such as cetylalcohol or wool wax for improving the water absorption. Emulsifiers arecorresponding lipophilic substances, such as sorbitan fatty acid ester.In addition, the ointments contain moisturisers such as polyalcohols,for example glycerol, propylene glycol, sorbitol and/or polyethyleneglycol as well as preservatives.

Rich creams are anhydrous formulations and are produced on the basis ofhydrocarbon compounds, such as paraffin, natural or partially syntheticfats, for example coconut fatty acid triglycerides or preferablyhardened oils and glycerol partial fatty acid esters.

Pastes are creams and ointments containing powdered ingredients whichabsorb secretions, for example metal oxides, such as titanium dioxide orzinc oxide, and also tallow and/or aluminium silicates which bind themoisture or the absorbed secretion.

Foams are liquid oil-in-water emulsions in aerosol form. Hydrocarboncompounds are used, inter alia, for the oil-containing phase, forexample paraffin oil, fatty alcohols, such as cetyl alcohol, fatty acidesters, such as isopropylmyristate and/or waxes. Suitable emulsifiersare, inter alia, mixtures of emulsifiers having predominantlyhydrophilic properties, for example polyoxyethylenesorbitan fatty acidester, and also emulsifiers having predominantly lipophilic properties,for example sorbitan fatty acid ester. Commercially available additivesare usually additionally employed, for example preservatives.

Gels are, in particular, aqueous solutions or suspensions of activesubstances in which gel formers are dispersed or swelled, in particularcellulose ethers, such as methyl cellulose, hydroxyethyl cellulose,carboxymethyl cellulose or vegetable hydrocolloid, for example sodiumalginate, tragacanth or gum arabic. The gels preferably additionallycontain also polyalcohols, such as propylene glycol or glycerol asmoisturizers and wetting agents, such as polyoxyethylenesobitan fattyacid ester. The gels furthermore contain commercially availablepreservatives, such as benzyl alcohol, phenethyl alcohol, phenoxyethanoland the like.

As discussed above, the inventors have discovered that the amphotericpolymer performs very well as a silicone deposition agent. That is whencombined in shampoo or bodywash containing silicone, the amphotericpolymers effectively aids in the deposition of silicone onto keratinoussurfaces such as hair and skin thus heightening conditioning effects.

The inventive ter-polymer upon dilution as mentioned above may form ater-polymer/silicone aggregate or coacervate/optional benefit agent(such as fatty amines, fatty amine oxides or quaternary amines, oilycomponents, fatty acids, silicone or mixtures thereof), thus physicallydepositing the aggregate onto the skin or hair where the conditioningbenefit is desired.

The present amphoteric polymer may be used in a personal cleansingcomposition or a personal care composition at about 0.05 to about 5,about 0.1 to about 3, about 0.1 to about 0.75, about 0.1 to about 0.5weight percent of the total personal care or personal cleansingcomposition.

Conditioning Agents

In addition to the fatty amines, fatty amine oxides and quaternaryamines, other conditioning agents may be combined with the inventiveter-polymer. For example, conditioning agents useful herein includesilicones, oily or fatty materials such as hydrocarbons, fatty ester,silicones and cationic fatty materials such as the fatty amines, fattyoxides, fatty quaternaries suggested above.

Silicones

The most commonly used conditioning agents are silicones. The presentamphoteric polymer is effective as a silicone deposition aid withvirtually any silicone. The most commonly used silicones which aresuitable for use in personal cleansing or personal care compositions aretypically modified or unmodified polyorganosiloxanes, i.e.polyorganosiloxane oils or polyorganosiloxane gums or resins, in theirnative form or in the form of solutions in organic solvents oralternatively in the form of emulsions or microemulsions.

Among the polyorganosiloxanes which may be used in accordance with thepresent invention, mention may be made, in a non-limiting manner, of:

I. Volatile silicones: these have a boiling point of between 60 C and260 C. They are chosen from cyclic silicones containing from 3 to 7 andpreferably 4 to 5 silicon atoms. Examples of these areoctamethylcyclotetrasiloxane sold under the name VOLATILE SILICONE 7207″by Union Carbide or SILBIONE 70045 V2 by Rhone-Poulenc,decamethylcyclopentasiloxane sold under the name VOLATILE SILICONE715811 by Union Carbide, SILBIONE 70045 V5 by Rhone-Poulenc, as well asmixtures thereof. Mention is also made of cyclocopolymers such asdimethylsiloxane/methylalkylsiloxane, for instance VOLATILE SILICONEFZ3109 sold by the company Union Carbide, which is adimethylsiloxane/methyloctylsiloxane cyclocopolymer.II. Non-volatile silicones: these consist mainly of:(i) polyalkylsiloxanes; among the polyalkylsiloxanes which may mainly bementioned are linear polydimethylsiloxanes containing trimethylsilyl endgroups, such as, for example, and in a non-limiting manner, the SILBIONEoils of the 70047 series sold by Rhodia Chimie; the DC200 oils andSilicone emulsions such as DC-1664 from Dow Corning, and PDMSscontaining hydroxydimethylsilyl end groups;(ii) polyarylsiloxanes;(iii) polyalkylarylsiloxanes; mention may be made of linear and branchedpolymethylphenylsiloxanes, polydimethylmethylphenylsiloxanes andpolydimethyldiphenylsiloxanes, such as, for example, the oil RHODORSIL76311 from Rhodia Chimie;(iv) silicone gums; these are polydiorganosiloxanes with a molecularmass of between 200,000 and 5,000,000, which are used alone or as amixture in a solvent chosen from volatile silicones,polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils,isoparaffins, methylene chloride, pentane, dodecane, tridecane,tetradecane or mixtures thereof; mention is made, for example, of thefollowing compounds:

-   -   polydimethylsiloxane,    -   poly[dimethylsiloxane)/(methylvinylsiloxane)],    -   poly[dimethylsiloxane)/(diphenylsiloxane)],    -   poly[(dimethylsiloxane)/(phenylmethylsiloxane)],    -   poly[dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)];        mention may also be made, for example, in a non-limiting manner,        of the following mixtures:        1) mixtures formed from a polydimethylsiloxane hydroxylated at        the end of a chain (Dimethiconol according to the CTFA        nomenclature) and from a cyclic polydimethylsiloxane        (Cyclomethicone according to the CTFA nomenclature), such as the        product Q2 1401 sold by the company Dow Corning;        2) mixtures formed from a polydimethylsiloxane gum with a cyclic        silicone, such as the product SF 1214 Silicone Fluid from        General Electric, which is an SE 30 gum of molecular        weight=500,000 is dissolved in SF 1202 Silicone Fluid        (decamethylcyclopentasiloxane);        3) mixtures of two PDMSs of different viscosity, in particular        of a PDMS gum and of a PDMS oil, such as the products SF 1236        and CF 1241 from General Electric;        (v) silicone resins; preferably crosslinked siloxane systems        containing R2SiO2/2, RSiO3/2 and Si4/2 units in which R        represents a hydrocarbon group containing 1 to 6 carbon atoms or        a phenyl group. Among these resins, mention may be made of the        product sold under the name Dow Corning 593;        (vi) organomodified polyorganosiloxanes; i.e. silicones as        defined above, comprising in their general structure one or more        organofunctional groups directly linked to the siloxane chain or        linked via a hydrocarbon based radical; mention is made, for        example, of silicones comprising:        a) polyethylenoxy and/or polypropylenoxy groups optionally        comprising alkyl groups, such as the product known as        dimethicone copolyol, sold by the company Dow Corning under the        name DC 1248, and alkyl (C12) methicone copolyol sold by the        company Dow Corning under the name Q2 5200;        b) (per) fluoro groups such as trifluoroalkyl groups, such as,        for example, those sold by the company General Electric under        the names FF.150 FLUOROSILICONE FLUID;        c) hydroxyacylamino groups, such as those described in European        patent application EP-A-0 342 834, and in particular the        silicone sold by the company Dow Corning under the name Q2-8413;        d) thiol groups, such as the silicones X 2-836 from Dow Corning        or GP 72A and GP 71 from Genesee;        e) substituted or unsubstituted amine groups, such as the        products sold under the name GP 4 Silicone Fluid and GP 7100 by        the company Genesee, or the products sold under the names Q2        8220 and Dow Corning 929 or 939 by the company Dow Corning. The        substituted amine groups are, in particular, C1-C4 aminoalkyl or        amino (C1-C4) alkylamino (C1-C4)alkyl groups. The silicones        known as amodimethicone and trimethylsilylamodimethicone        according to the CTFA name (1997) are used more particularly;        f) carboxylate groups, such as the products described in        European patent EP 186 507 from Chisso Corporation;        g) hydroxyl groups, such as the polyorganosiloxanes containing a        hydroxyalkyl function, described in patent application FR-A-2        589 476;        h) alkoxy groups containing at least 12 carbon atoms, such as        the product SILICONE COPOLYMER F 755 from SWS Silicones;        i) acyloxyalkyl groups containing at least 12 carbon atoms, such        as, for example, the polyorganosiloxanes described in patent        application FR-A-2 641 185;        j) quaternary ammonium groups, such as in the product ABIL K        32701 from the company Goldschmidt;        k) amphoteric or betaine groups, such as in the product sold by        the company Goldschmidt under the name ABIL B 9950;        l) bisulfite groups, such as in the products sold by the company        Goldschmidt under the names ABIL S 201 and ABIL S 255;        (vii) block copolymers containing a linear        polysiloxane-polyalkylene block as repeating unit; the        preparation of such block copolymers used in the context of the        present invention is described in European patent application EP        0 492 657 A1, the teaching of which is included by way of        reference in the present description;        (viii) grafted silicone polymers, containing a non-silicone        organic skeleton, consisting of a main organic chain formed from        organic monomers containing no silicone, onto which is grafted,        within the said chain as well as, optionally, on at least one of        its ends, at least one polysiloxane macromonomer; in particular        those chosen more preferably from those described in U.S. Pat.        Nos. 4,963,935, 4,728,571 and 4,972,037 and patent applications        EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578,        the teachings of which are included in their entirety in the        present description by way of non-limiting references;        (ix) grafted silicone polymers, containing a polysiloxane        skeleton grafted with non-silicone organic monomers, comprising        a main polysiloxane chain onto which is grafted, within the said        chain as well as, optionally, on at least one of its ends, at        least one organic macromonomer containing no silicone; examples        of such polymers, and the particular method for preparing them,        are described in particular in patent applications EP-A-0 582        152, WO 93/23009 and WO 95/03776, the teachings of which are        included in their entirety in the present description by way of        non-limiting references;        (x) or mixtures thereof.

The polyorganosiloxanes preferably used according to the invention arenon-volatile polyorganopolysiloxanes and preferably polydimethylsiloxaneoils or gums that are optionally aminated, arylated or alkylarylated.

Copending U.S. Ser. No. 12/286,260 herein incorporated entirely byreference describes a modified silicone. The present ampholyticter-polymer may be used in combination with the therein taught siliconederivatives as an effective deposition aid in personal carecompositions.

The polyorganosiloxanes are used in the compositions of the invention inproportions of between 0.01% and 20% by weight and preferably between0.1 and 10% by weight, relative to the total weight of the composition.

Non-Silicone Conditioning Agents

Compositions according to the present invention may comprise adispersed, non-volatile, water-insoluble oily non-silicone conditioningagent.

Suitable oily or fatty materials are selected from hydrocarbon oils,fatty esters and mixtures thereof.

Straight chain hydrocarbon oils may for example contain from about 12 toabout 30 carbon atoms. Also suitable are branched chain hydrocarbon oilswill preferably contain from about 12 to about 42 carbon atoms. Alsosuitable are polymeric hydrocarbons of alkenyl monomers, such as C₂-C₆alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil,mineral oil, saturated and unsaturated dodecane, saturated andunsaturated tridecane, saturated and unsaturated tetradecane, saturatedand unsaturated pentadecane, saturated and unsaturated hexadecane, andmixtures thereof. Branched-chain isomers of these compounds, as well asof higher chain length hydrocarbons, can also be used. Another suitablematerial is polyisobutylene.

Suitable fatty esters are characterised by having at least 10 carbonatoms, and include esters with hydrocarbyl chains derived from fattyacids or alcohols, Monocarboxylic acid esters include esters of alcoholsand/or acids of the formula R¹COOR in which R* and R independentlydenote alkyl or alkenyl radicals and the sum of carbon atoms in R^(f)and R is at least 10, preferably at least 20. Di- and trialkyl andalkenyl esters of carboxylic acids can also be used.

The viscosity of the conditioning oil itself (not the emulsion or thefinal hair conditioning composition) is from 350 to 10,000,000 mrr^sec″¹at 25° C.

The oily or fatty material is suitably present at a level of from 0.05to 20, preferably from 0.2 to 10, more preferably from about 0.5 to 5percent by weight of the composition.

Humectants and Moisturizers

The compositions of the present invention can contain one or morehumectant or moisturizing materials. A variety of these materials can beemployed and each can be present at a level of from about 0.1% to about20%, more preferably from about 1% to about 10% and most preferably fromabout 2% to about 5%. These materials include urea; guanidine; glycolicacid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium);lactic acid and lactate salts (e.g. ammonium and quaternary alkylammonium); aloe vera in any of its variety of forms (e.g., aloe veragel); polyhydroxy alcohols such as sorbitol glycerol, hexanetriol,propylene glycol, butylene glycol, hexylene glycol and the like;polyethylene glycols; sugars and starches; sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid; lactamidemonoethanolamine; acetamide monoethanolamine; and mixtures thereof.Preferred humectants and moisturizers are glycerol, butylene glycol,hexylene glycol, and mixtures thereof.

Detersive Surfactants

These ampholyte polymers of the invention are particularly compatiblewith detersive anionic surfactant-containing products such as those usedin shampoos or personal cleansing products, generally providing clearformulations without the loss of conditioning properties described abovebut are also compatible with cationic, nonionic, zwitterionic oramphoteric surfactants.

Suitable anionic detersive surfactant components for use in the shampoocomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic detersive surfactant component in the shampoo composition shouldbe sufficient to provide the desired cleaning and lather performance,and generally for example in the range from about 5% to about 50%, fromabout 8% to about 30%, from about 10% to about 25% and from about 12% toabout 18%, by weight of the composition.

Preferred anionic surfactants suitable for use in the shampoocompositions are the alkyl and alkyl ether sulfates. These materialshave the respective formulae ROSO₃M and RO(C₂H₄O)_(x)SO₃— M, wherein Ris alkyl or alkenyl of from about 8 to about 18 carbon atoms, x is aninteger having a value of from 1 to 10, and M is a cation such asammonium, alkanolamines, such as triethanolamine, monovalent metals,such as sodium and potassium, and polyvalent metal cations, such asmagnesium, and calcium.

R typically has from about 8 to about 18 carbon atoms, from about 10 toabout 16 carbon atoms, from about 12 to about 14 carbon atoms, in boththe alkyl and alkyl ether sulfates. The alkyl ether sulfates aretypically made as condensation products of ethylene oxide and monohydricalcohols having from about 8 to about 24 carbon atoms. The alcohols canbe synthetic or they can be derived from fats, e.g., coconut oil, palmkernel oil, tallow. Lauryl alcohol and straight chain alcohols derivedfrom coconut oil or palm kernel oil are preferred. Such alcohols arereacted with between about 0 and about 10, about 2 to about 5, about 3,molar proportions of ethylene oxide, and the resulting mixture ofmolecular species having, for example, an average of 3 moles of ethyleneoxide per mole of alcohol, is sulfated and neutralized.

Other suitable anionic detersive surfactants are the water-soluble saltsof organic, sulfuric acid reaction products conforming to the formula[R₁—SO₃-M] where R₁ is a straight or branched chain, saturated,aliphatic hydrocarbon radical having from about 8 to about 24, about 10to about 18, carbon atoms; and M is a cation described hereinbefore.

Still other suitable anionic detersive surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil or palm kernel oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the fatty acids, for example, arederived from coconut oil or palm kernel oil.

Typical specific anionic detersive surfactants for use in the personalcleansing compositions include ammonium lauryl sulfate, ammonium laurethsulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate,triethanolamine lauryl sulfate, triethanolamine laureth sulfate,monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauricmonoglyceride sodium sulfate, sodium lauryl sulfate, sodium laurethsulfate, potassium lauryl sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate,sodium dodecyl benzene sulfonate, and combinations thereof.

Suitable amphoteric or zwitterionic detersive surfactants may be used inthe personal cleansing compositions and herein include those which areknown for use in hair care or skin care cleansing composition, and whichcontain a group that is anionic at the pH of the cosmetic (such as ashampoo) composition. Concentration of such amphoteric detersivesurfactants range for example from about 0.5% to about 20%, from about1% to about 10%, by weight of the composition.

Amphoteric detersive surfactants suitable for use in the personalcleaning compositions are well known in the art, and include thosesurfactants broadly described as derivatives of aliphatic secondary andtertiary amines in which the aliphatic radical can be straight orbranched chain and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionic watersolubilizing group such as carboxy, sulfonate, sulfate, phosphate, orphosphonate.

Zwitterionic detersive surfactants suitable for use in personal cleaningcomposition are well known in the art, and include those surfactantsbroadly described as derivatives of aliphatic quaternary ammonium,phosphonium, and sulfonium compounds, in which the aliphatic radicalscan be straight or branched chain, and wherein one of the aliphaticsubstituents contains from about 8 to about 18 carbon atoms and onecontains an anionic group such as carboxy, sulfonate, sulfate, phosphateor phosphonate. Zwitterionics such as betaines are also envisioned.

The personal cleaning compositions of the present invention may furthercomprise additional surfactants for use in combination with the anionicdetersive surfactant component described hereinbefore. Suitable optionalsurfactants include nonionic surfactants, cationic surfactants, andcombinations thereof. Any such surfactant known in the art for use inhair or personal care products may be used, provided that the optionaladditional surfactant is also chemically and physically compatible withthe essential components of the personal cleaning composition, or doesnot otherwise unduly impair product performance, aesthetics orstability. The concentration of the optional additional surfactants inthe personal cleaning composition may vary with the cleansing or latherperformance desired, the optional surfactant selected, the desiredproduct concentration, the presence of other components in thecomposition, and other factors well known in the art.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the personalcleansing or shampoo compositions are described in McCutcheon's,Emulsifiers and Detergents, 1989 Annual, published by M. C. PublishingCo. which descriptions are incorporated herein by reference.

An especially preferred embodiment of the invention is a personalcleansing or personal care composition comprising the conditioningpolymer, wherein the conditioning polymer is dispersed or solubilized ina cosmetically acceptable vehicle and optionally further comprises atleast one surfactant chosen from anionic, amphoteric, nonionic andzwitterionic surfactants.

An even more preferred embodiment is a personal cleansing or personalcare composition, wherein the personal cleansing composition comprisingthe conditioning polymer is a shampoo or a bodywash and the personalcare composition is any personal care composition which is applied tothe body, including the skin and hair.

The personal cleansing composition of special interest is a cleansingcomposition which for example may be s a 2-in-1 shampoo, a bodywash, afacial wash, a bubble bath, soapless cleansers, liquid and bar soap; ashower gel, exfoliating shower gel; a milk bath; moist towelletes; batheffervescent tablets (e.g., bubble bath); a bath/shower gel or a showercream, preferably the cleansing composition is a 2-in-1 shampoo and thepersonal cleansing composition optionally further comprises a detersiveanionic surfactant from 5% to 50%, preferably from 8% to 30%, mostpreferably from 10% to 25% and especially 12% to 18%, by weight of thecomposition.

Benefit Agents

Benefit agents may be combined with the inventive ter-polymer andoptionally include conditioning agents such as hydrocarbon oils, fattyesters, silicones, fatty amines, fatty amine oxides and fattyquaternaries. Further benefit agents possible may also include suchingredients as sunscreens, anti dandruff agents, proteins, minerals,herbal extracts, pediculocides, vitamins and UV absorbers.

Optional Ingredients

Further, it is common for personal care preparations to containsuspending agents, viscosity modifiers, dyes, nonvolatile solvents ordiluents (water soluble and insoluble), pearlescent aids, foam boosters,additional surfactants or nonionic cosurfactants, pH adjusting agents,perfumes, preservatives, chelants, skin active agents, minerals,herbal/fruit/food extracts, sphingolipids derivatives or syntheticalderivative, and clay.

Anti-dandruff agents are of particular interest as cationic polymers arewell known as aids for deposition of anti-dandruff agents such aspyridinethione salts. For example, U.S. Publication Application Nos.2008/0206355 teaches cationic homopolymers in combination pyrithione.Thus the compositions of the present invention may also contain ananti-dandruff agent.

Suitable, non-limiting examples of anti-dandruff particulates include:pyridinethione salts, azoles, selenium sulfide, particulate sulfur, andmixtures thereof. Preferred are pyridinethione salts. Such anti-dandruffparticulate should be physically and chemically compatible with theessential components of the composition, and should not otherwise undulyimpair product stability, aesthetics or performance.

Pyridinethione anti-dandruff particulates, especially1-hydroxy-2-pyridinethione salts, are highly preferred particulateanti-dandruff agents for use in compositions of the present invention.The concentration of pyridinethione anti-dandruff particulate typicallyranges from about 0.1% to about 4%, by weight of the composition,preferably from about 0.1% to about 3%, more preferably from about 0.3%to about 2%. Preferred pyridinethione salts include those formed fromheavy metals such as zinc, tin, cadmium, magnesium, aluminum andzirconium, preferably zinc, more preferably the zinc salt of1-hydroxy-2-pyridinethione (known as “zinc pyridinethione” or “ZPT”),more preferably 1-hydroxy-2-pyridinethione salts in platelet particleform, wherein the particles have an average size of up to about 20microns, preferably up to about 5 microns, more preferably up to about2.5 microns. Salts formed from other cations, such as sodium, may alsobe suitable.

The personal care or personal cleansing compositions containing theinventive ter-polymer may additionally contain further polymers. Thefurther polymer may for example, be:

-   -   homopolymer of polyacrylamide of molecular weight ranging from        about 1,000,000 to about 30,000,000, about 2,000,000 to about        8,000,000 or about 2,000,000 to about 5,000,000.    -   a cationic copolymer different than the inventive ter-polymer.        For example, the cationic copolymer may be a copolymer of        acrylamide and cationic monomers such as        (meth)acryloyloxyethyl-N,N,N-trimethylammonium chloride,        -(meth)acryloyloxyethyl-N-ethyl-N,N-dimethylammonium monoethyl        sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl        sulfate, -(meth)acryloylaminopropyl-N,N,N-trimethylammonium        chloride, (meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium        monoethyl sulfate,        (meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium chloride        or (meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium        monomethyl sulfate or mixtures thereof.

The second cationic copolymer will typically contain from 0.1 to about25 weight percent, 4 to about 20 or about 5 or about 20 weight percentcationic monomer based on the total weight of the copolymer.

Preparation of the Ter-Polymer

The amphoteric conditioning polymers can be prepared in the conventionalmanner, e.g., by mass or solution polymerization. The polymerization maytake place in an aqueous, solvent or aqueous-solvent mixed environmentbut it is preferred that the reaction be carried out in a substantiallyaqueous environment. Possible solvents are DMSO, THF, DMF, ethyl,propyl, butyl, acetate, benzene, toluene, xylene, N-butanol, isobutanol,isopropanol, MEK, MIBK, acetone, etc.

It is preferred to carry out the polymerization in the absence ofoxygen.

The monomers are preferably polymerized using a radical reaction, byaddition of peroxides, optionally in the presence of redox systems.Initiators such as ammonium persulfate are ideal as this initiator ishighly water soluble.

The polymerization time of the conditioning polymer depends on thetemperature and the desired final product properties but is preferablywithin the range of from 0.5 to 10 hours at temperatures ranging fromabout 50° C. to about 190° C. The polymerization can be carried outcontinuously, discontinuously or semicontinuously. If it is preferred toobtain a polymer chain having random distribution of monomers, all ofthe monomers together will be preferably added to the reaction mixture.This may be done in one portion or metered over time to control the rateof the reaction.

On the basis of the reactivity of the monomers, which is known, askilled artisan can control the polymerization so as to obtain thedesired distribution.

EXAMPLES

Determination of average molecular weight is carried out by gelpermeation chromatograph.

Key to Abbreviations

APTAC—acryloylaminopropyl-N,N,N-trimethylammonium chloride

EGDS—ethylene glycol distearate

DAA—diallyamine

ADAA—Alkoxylated Diallyamine—These monomers are prepared according tothe examples of U.S. Pat. Nos. 7,579,421 and 5,478,883 hereinincorporated entirely by reference

NaEDTA—sodium salt of ethylene diamine tetra acetic acid

Cocamide MEA—Cocamide Monoethanolamine

SLS—Sodium Lauryl Sulfate

SLES-X, Sodium Laureth Sulfate with X moles of ethoxylation

EO/PO—ethoxy/propoxy groups

VA 044—2,2′-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride

tBHP— tert butyl hydrogen peroxide

SMBS—Sodium metabisulfite

HLB—hydrophilic-lipophilic balance

Synthesis of Amphoteric Conditioning Polymer Example 1 Preparation ofAPTAC/AA/DAA Ter-Polymer

Reactor Charge (RC) 75% APTAC 0.7 g 97% DAA 3.5 g 99% Acrylic Acid 0.1 g10% NaEDTA 1.0 g Deionized Water 160 g  Adjust pH to 4.0 using HCL (5%)solution

Monomer Feed (MF)   75% APTAC 114 g    97% DAA 0.6 g    99% Acrylic Acid10 g 0.10% methylenebisacrylamide 30 g Adjust pH to 4.0 using NaOHsolution

A one liter reactor is purged with nitrogen. The RC charge is added tothe reactor. The reactants are stirred at 210 rpm and heated to 100° C.The intiator (ammonium persulfate, 0.2 g in 20 ml water) is introducedat a rate of 0.22 ml/min while the remaining monomer feeds (MF) is addedover a period of 60 min. After the addition of monomer feeds, thecontainer is rinsed with 10 mL DI water. The initiator is fed at thesame rate. After the addition of initiator is completed, the batch isheld at 100° C. for 0.5 hr. Then Sodium metabisulfite (1 wt % aqueoussolution, 2.6 mL) is added at the rate of 0.5 ml/min. The batch is thenmaintained at 100° C. for another 0.5 hr. The resulting polymer hasweight ratios respectively of APTAC/AA/DAA or 86/10/4. MW 210 K

Optional Neutralization of the Formed Amphoteric Conditioning Polymer

The reactor is cooled to about 60° C. Before discharging the polymerfrom the reactor a fatty amine or fatty amine oxide is optionally addedfor example at weight ratios ranging between 0.5:2 to 1:2 (fatty amineto conditioning polymer). The mixture is stirred thoroughly to allow forproduct homogeneity and neutralization. The fatty amines, fatty amineoxides or fatty quaternary used for neutralization are dodecylamine,dodecyldimethyl amine, dodecyldimethyl amine oxide, myristylamine,myristyldimethyl amine, myristyldimethyl amine oxide, stearylamine,stearyldimethyl amine, stearyldimethyl amine oxide and cetyltrimethylammonium Chloride. After neutralization, the polymer is discharged fromthe reactor

The reactor is cooled to about 60° C. Before discharging the polymerfrom the reactor a dodecylamine is optionally added at weight ratio of1:2 (fatty amine:conditioning polymer). The mixture is stirredthoroughly to allow for product homogeneity. After neutralization, thepolymer is discharged from the reactor.

See Table I for further examples 2-8 containing APTAC:AA:DAA.

Example 9 Preparation of APTAC/AA/DAA-alkoxylated Ter-Polymer

Reactor Charge (RC) Weight, g 1. 60% APTAC 2 2. DAA-EO/PO 90:10 wt.Ratio¹ 22.64 3. Acrylic Acid 0.2 4. NaEDTA 0.2 5. Citric acid 1 g 6. HCl(10%) to adjust pH to 4 7. Deionized water (DIW) 250 + 30 (rinse)

Monomer feed (MF) Weight, g  8. 60% APTAC 293  9. Acrylic Acid 20 10.MBA (0.1 wt %) 60 (300 ppm) 11. DI water 40 + 20 (rinse) Adjust pH to 4using 1N NaOH

Weight, g Initiator feed (IF) 12. tBHP (1 wt %) 20 g 13. SMBS (1 wt %)20 g Post treatment (PT) 14. VA 044 (200 PPM) 40 mg

A terpolymer of 80.6:9.1:10.3 weight ratio of APTAC:AA:DAA-EO/PO isformed.

1. Mw is 1100.

Example 10

Reactor Charge (RC) Weight, g 15. 75% APTAC 1.4 16. DAA -EO/PO 80/20¹ 3017. Acrylic Acid 0.1 18. NaEDTA 0.1 19. Citric acid 0.5 20. HCl (10%) toadjust pH to 4 21. Deionized water (DIW) 50 + 20

Monomer feed (MF) Weight, g 22. 75% APTAC 117 23. Acrylic Acid 10 24.MBA (0.1 wt %) 30 25. DI water 50 + 10 Adjust pH to 4 using 1N NaOH

Initiator feed (IF) Weight, g 26. tBHP (0.75 wt %) 20 g 27. SMBS (0.75wt %) 20 g

Post treatment (PT) Weight, g 28. VA 044 (200 PPM) 40 mg

A terpolymer of 68.9:7.8:23.3 weight ratio of APTAC:AA:DAA-EO/PO isformed.

1. Mw is 3000.

Procedure

The procedure for examples 2 and 3 are substantially as in example 1above but a combination of initiators are used (t-BHP and SMBS).

Amphoteric Polymers

Various amphoteric polymers prepared as above in example 1 but ratios ofAPTAC, Acrylic acid and DAA and all with a Mw of ˜210K are varied alongwith neutralization with different fatty amines.

TABLE 1 Amphoteric polymers formed from APTAC/AA/DAA. DAA AA APTAC (wt.(wt. Mw Example (wt. %) %) %) Amine X-Link (×1000) 1 86 4 10dodecylamine yes ~210 2 96 4 0 dodecylamine yes ~215 3 56 4 40dodecylamine yes ~210 4 86 4 10 Dodecyldimethyl no ~210 amino oxide 5 8010 10 NA no ~195 6 86 4 10 Cetyltrimethyl yes ~205 ammonium Chloride 750 10 40 dodecylamine no ~215 8 60 15 25 NA No ~210

TABLE 2 ADAA Properties EO/PO APTAC:AA:DAA ADAA Ratio Mw Example (molarratio) (mol %) HLB (MW) XLink (×1000) 9 72.9:25.2:0 1.9 8 90/10 Yes 434(1100) 10 72.9:25.2:0 1.9 17 80/20 Yes 300 (3000) 11 72.9:25.2:1.9 0 — —Yes 728 12 71.7:24.8:1.7 1.8 17 80/20 Yes 471 (3000) 13 72.9:25.2:0 1.917 80/20 Yes NA (3000) 14 72.9:25.2:0 1.9 8 90/10 Yes 198 (1100) 1572.9:25.2:0 1.9 9 90/10 Yes 552 16 95.3:0:0 4.7 17 80/20 Yes  55 (3000)17 72.9:25.2:0 1.9 17 80/20 Yes 223 (3000) 19 72.9:25.2:0 1.9 8 90/10Yes 435 (1100) 20 42.1:56.5:0 1.4 17 80/20 Yes 142 (3000)Personal Cleansing Formulation of the Conditioning Polymer

For the shampoos below, all ingredients are mixed and heated to about70° C. and homogenized to improve dispersability of silicon and theconditioning ter-polymer/fatty amine complex. Before cooling, NaCl andcitric acid are added if necessary to adjust for a viscosity rangingbetween 7000-8000 cps at room temperature and for a pH of 5.7.

Shampoo 1 Ingredient Wt. Percent Sodium Lauryl Ether-2 Sulfate 12.00 (2moles of ethoxylation) Coacamidopropyl Betaine 3.00 EGDS 2.00Conditioning Polymer (examples 1-20) 0.25 (active polymer) Dodecylamine0.0 to 0.12% Water Qs

Shampoo 2 Ingredient Wt. Percent Sodium Lauryl Ether-2 Sulfate 12.00 (2moles of ethoxylation) Coacamidopropyl Betaine 3.00 EGDS 2.00Conditioning Polymer (examples 1-20) 0.25 (active polymer) LauramineOxide 0.0 to 0.12% Water Qs

Shampoo 3 Ingredient Wt. Percent Ammonium Laureth-3 Sulfate 10.00Ammonium Lauryl Sulfate 4.00 Coacamidopropyl Betaine 3.00 Cocamide MEA1.00 EGDS 2.00 Conditioning Polymer (examples 1-20) 0.25 (activepolymer) Dodecylamine 0.0 to 0.12 Water Qs

Shampoo 4 Ingredient Wt % Sodium Lauryl Ether-2 Sulfate 12.00 (2 molesof ethoxylation) Cocamidoproyl Betaine 3.0 Silicone DC-1664 (Dow) 2.0EGDS 2.0 Conditioning Polymer (examples 1-20) 0.0 to 0.25 (activepolymer) Dodecylamine 0.0 to 0.12 Water Qs

Body Wash Ingredient Wt % Sodium Laureth-2 Sulfate 8.0 CocamidopropylBetaine 2.0 Disodium Laureth Sulfosuccinate 1.0 PEG-7 Glyceryl Cocoate0.5 Conditioning Polymer (examples 1-20) 0.25 Water Qs

Moisturizing Hand Lotion Ingredient Wt % Cetostearyl alcohol (50/50)5.00 Myristyl Myristate 5.0 Methyl Glucose Sesquistearate 0.8 IsopropylMyristate 4.0 Conditioning Polymer (examples 1-20) 0.25 (active polymer)Tween 60 2.6 PEG-20 Methyl Glucose 1.50 White Ceresine Wax 0.4Triethanol amine 0.20 Arlacel 60 3.0 Water Qs

Liquid Soap Ingredient Wt % Sodium laureth sulfate   10-15.00Cocamidoproyl Betaine 15-20 Silicone DC-1664 (Dow) 2.0 Sunflower SeedOil 2.0 Conditioning Polymer (examples 1-20) 0.25 (active polymer)Sorbitan monolaurate 1-3 Hydantoin (preservative) 0.2 Fragrance 1.0Styrene Acrylate (opacifier) 0.4 Water Qs

Shower Gel Ingredient Wt % Sodium Lauroamphoacetate 7 Sodium LaurethSulfate 14 Cetyl Acetate and Acetylated Lanolin .5 Alcohol Lauric acid2.5-3.0 Sunflower Seed Oil 3.0 Vitamin E 1.0 Conditioning Polymer(examples 1-20) 0.25 (active polymer) Cocamide Monoethanol amide 2 GuarHydroxypropyl trimonium chloride 0.5 Glycerin 2 Hydantoin (preservative)0.2 Fragrance 1.0 Titanium dioxide 0.2 Water QsApplication Data

The ter-polymers are formulated into the following shampoo compositionfor determining their silicone deposition on hair, polymer conditioningeffects and reduction in combing energies.

Ingredient Wt % Sodium Lauryl Ether-2 Sulfate 10.00 (2 moles ofethoxylation) SLS 4.0 Cocamide MEA 1.0 Cocamidoproyl Betaine 3.0Sillicone DC-1664 (Dow) 1.0 EGDS 2.0 Conditioning Polymer (example 1)0.25 (active polymer) Dodecylamine 0.12 Water QsSilicone Deposition

Washing Procedure

Ten virgin brown hair tresses are weighed and treated for each shampooto be tested. Five of the tresses are shampooed twice and five areshampooed ten times. Each tress is pre-washed with 15% TERGITOL rinsedthoroughly and then wet with water.

1 g of shampoo is applied down the length of each tress and lathered.The tresses are rinsed in a flow of tap water (0.4 gallon per minute)for one minute at 35 C. The hair is allowed to dry overnight at roomtemperature conditions and is then ready for silicone extraction.

Silicone Analysis of Hair

The treated tresses are extracted with 30 ml of a toluene/methylisobutylketone (50/50) mixture in glass centrifuge tubes.

Quantitative analysis of silicone is carried out using an atomicabsorption analyzer equipped with a graphite furnace (Perkin ElmerAAnalyst 600).

The hair washing analysis and extractions are carried out in triplicate.Furthermore, the hair washing analysis and extractions are repeated twoand fourteen days after preparation of the shampoo in order to determinethe stability of the shampoos performance upon storage.

Polymer Conditioning Effects

The washing procedure is carried out similarly to washing proceduredescribed above except 9 gram hair tresses, 8 inches long are washedwith 2 grams of shampoo. The hair tresses are European brown fromInternational Hair Importers.

The inventive ter-polymers/fatty amine complexes show improved feel andless “squeakiness”. The absence or lowering of “squeakiness” isconsidered an important advantage in 2 and 1 shampoos.

Dry and Wet Combing Energies

Reductions in dry and wet combing energies are measured using aDIA-STRON MINIATURE TENSILE TESTER MTTL75.

The wet combing energies are determined by immersing the treated tressesin a beaker of water three times and squeezing out excess water usingfingers.

The dry combining energies are determined analogously except the tressesare air dried before measurements.

Table 2

Application Results Containing Various Ter-Polymers

TABLE 3 Results for Ter-Polymers Containing DAA Reduction in Reductioncombing in wet friction friction Silicon Energy¹ energy² ExampleDeposition μg/g (%) (%) Control/No 26 0 0 polymer 1 389 71 68 2 432 6265 3 394 51 48 ¹Dry hair 9.7% Standard Deviation ²Wet hair 10.7%Standard Deviation

TABLE 4 Results for Ter-Polymers Containing Alkoxylated DAA Reduction inReduction combing in wet friction friction Silicon Energy¹ energy²Example Deposition μg/g (%) (%) Control/No ~26 0 0 polymer 9 398 71 6110 243 58 54 11 432 59 57 12 378 72 65 13 343 59 62 14 168 63 58 15 41283 72 16 <12 34 21 17 173 61 57 18 <12 27 30 19 411 69 57 20 146 37 34¹Dry hair 11.7% Standard Deviation ²Wet hair 10.4% Standard Deviation

The invention claimed is:
 1. A conditioning polymer formed from i) acationic monomer defined by formula (I)

in which: R₁ and R₂ are independently hydrogen or methyl, R₃, R₄ and R₅are independently linear or branched C₁-C₃₀ alkyl radicals, X is NH orNR₆, R₆ is C₁-C₆ alkyl, L is C_(n)H_(2n), n is an integer from 1 to 5,and A⁻ is an anion derived from an organic or inorganic acid; ii) atleast one anionic monomer selected from the group consisting ofethylenically unsaturated carboxylic acid and sulfonic acid containingmonomers; and iii) a diallyl amine monomer defined by formulae (II) or(III)

in which, R₇ and R₈ are independently hydrogen or C₁-C₄ alkyl, R₉ isC₁-C₃₀alkoxy,

hydroxy substituted C₁-C₁₀ alkyl, C₇-C₉alkylphenyl, carboxyalkyl,alkoxyalkyl, or carboxyamidalkyl, R₁₀ is hydrogen, C₁-C₂₀ alkyl, C₅-C₁₀cycloalkyl or an unsubstituted benzyl radical, with the proviso that ifR₁₀ is other than hydrogen, then R₉ is

AO is a C₁-C₁₂ alkylene oxide or a mixture of two or more differenttypes of C₁-C₁₂ alkylene oxides, it being possible for the two or moredifferent C₁-C₁₂ alkylene oxides to be attached to one another in blockform or in random form, m is an integer from 1 to 200, R₁₁ is hydrogenor methyl; and iv) optionally, a crosslinking monomer.
 2. Theconditioning polymer according to claim 1, wherein the cationic monomerof formula (I) is selected from the group consisting of(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride,(meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium monoethylsulfate, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniumchloride, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammoniummonomethyl sulfate and mixture thereof.
 3. The conditioning polymeraccording to claim 1, wherein the monomer of formula (I) makes up about10 to about 98 weight percent of the total weight of the formedter-polymer.
 4. The conditioning polymer according to claim 1, whereinthe anionic monomer of component ii) makes up about 2 to about 25 weightpercent of the total weight of the formed polymer.
 5. The conditioningpolymer according to claim 1, wherein the molar ratio of the monomerunits of components i) and ii) vary from about 12:1 to about 3:1 in theformed ter-polymer.
 6. The conditioning polymer according to claim 1,wherein the diallyl amine monomer of formulae (II) or (III) makes upfrom about 2 to about 40 weight percent of the total weight of theformed ter-polymer.
 7. The conditioning polymer according to claim 1,wherein the anionic monomer of component ii) is a compound of formula(VI) or an anhydride thereof:

R₁₂ and R₁₃ are independently hydrogen or C₁-C₆alkyl, R₁₄ is hydrogen,C₁-C₆alkyl or a COOM group, M is hydrogen, a monovalent or divalentmetal ion, ammonium or an organic ammonium ion, and R₉ and R₁₀ of thediallyl component iii) are hydrogen.
 8. The conditioning polymeraccording to claim 1, wherein component iii) is a compound of formulae(11a) and/or (111a)

wherein AO is a C₁-C₁₂ alkylene oxide or a mixture of two or moredifferent C₁-C₁₂ alkylene oxides, it being possible for the two or moredifferent C₁-C₁₂ alkylene oxides to be attached to one another in blockform or in random form, m is an integer from 1 to 200, and R₁₁ ishydrogen or methyl.
 9. The conditioning polymer according to claim 8,wherein the average molecular weight of the monomer of (11a) and (111a)varies from about 500 to about
 3500. 10. The conditioning polymeraccording to claim 8, wherein the hydrophilic-lipophilic balance of themonomer of formula (11a) or (111a) is between about 5 to about
 18. 11.The conditioning polymer according to claim 8, wherein the monomer offormula (11a) or (111a) is formed by the reaction of diallyamine withabout 10 to about 30 wt. percent propylene oxide and about 90 to about70 wt. percent ethylene oxide, wherein the wt. percent is based on thetotal weight of the monomer of formula (11a) or (111a).
 12. Theconditioning polymer according to claim 1, wherein the conditioningpolymer has an average molecular weight of about 10,000 to about18,000,000.
 13. The conditioning polymer according to claim 1, whereinthe conditioning polymer is crosslinked.
 14. The conditioning polymeraccording to claim 1, wherein the total charge density of the formedter-polymer varies from about 0.2 to about 7 mequiv./gram.
 15. Theconditioning polymer according to claim 1 in addition to monomers i),ii), iii) includes a non-ionic monomer iv) selected from the groupconsisting of C₁-C₂₂ straight or branched chain alkyl acrylates, C₁-C₂₂straight or branched chain alkyl methacrylates, C₁-C₂₂ straight orbranched chain n-alkyl acrylamides, C₁-C₂₂ straight or branched chainn-alkyl methacrylamide, C₁-C₆ hydroxy substituted alkyl acrylates, C₁-C₆hydroxy substituted alkyl methacrylates, n-vinylpyrrolidone, vinylacetate, ethoxylated or propoxylated acrylate, ethoxylated orpropoxylated methacrylate and unsubstituted acrylamide.
 16. A method forenhancing the deposition of silicone to skin, hair or nails comprisingthe steps of topically applying a composition comprising i) theconditioning polymer according to claim 1, ii) a silicone compound andoptionally, iii) an effective amount of a benefit agent to a desiredlocation on the skin, hair or nails.
 17. A conditioning polymer formedfrom i) a cationic monomer defined by formula (I)

in which: R₁ and R₂ are independently hydrogen or methyl, R₃, R₄ and R₅are independently linear or branched C₁-C₃₀ alkyl radicals, X is NH, NR₆or oxygen, R₆ is C₁-C₆ alkyl, L is C_(n)H_(2n), n is an integer from 1to 5, and A⁻ is an anion derived from an organic or inorganic acid; ii)at least one anionic monomer selected from the group consisting ofethylenically unsaturated carboxylic acid and sulfonic acid containingmonomers; iii) a diallyl amine monomer defined by formulae (11a) or(111a)

wherein R₇ and R₈ are independently hydrogen or C₁-C₄ alkyl, AO is aC₁-C₁₂ alkylene oxide or a mixture of two or more different C₁-C₁₂alkylene oxides, it being possible for the two or more different C₁-C₁₂alkylene oxides to be attached to one another in block form or in randomform, m is an integer from 1 to 200, and R₁₁ is hydrogen or methyl; and(iv) optionally, a crosslinking monomer.